DE112005002727T5 - Thermoplastic resin composition and molded article - Google Patents

Abstract

Thermoplastic resin composition comprising:
(A) a resin composition comprising (a-1) a polycarbonate resin in an amount of 45 to 97 mass% and (a-2) a fatty acid polyester in an amount of 55 to 3 mass% and
(B) a rubbery elastomer in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the resin mixture, wherein component (B) is present in an interface between component (a-1) and component (a-2) or domains of component ( a-2) is dispersed.

Description

Area of Expertise

The The present invention relates to a thermoplastic resin composition. In particular, the present invention relates to a thermoplastic Resin composition, the high impact resistance characteristics and high fluidity that has the flaws in appearance, such as pearlescent shine and turbulence impressions, fixes.

The Thermoplastic resin composition is in the field of electrical and electronic devices, like office automation systems, Information and communication appliances and household electrical appliances the field of motor vehicles, in the construction sector, etc. applicable.

State of technology

Currently finds a polycarbonate / polylactic acid alloy in terms of the reduction of environmental impact attention, since the polylactic acid a is resin derived from plants.

polycarbonate has a low fluidity on. Will it be with polylactic acid alloyed, the polycarbonate, however, due to the high fluidity of polylactic acid, however effectively a high fluidity be lent.

Regarding the structure of polylactic acid It is believed that polylactic acid that is alloyed with polycarbonate is, when burning hardly produces a dangerous gas. Consequently is polylactic acid a resin that is expected to be in the field of office automation equipment and household electrical appliances is used when a flame retardancy standard is required.

conventional Polycarbonate / polyester alloy lacks fluidity, though they have excellent heat resistance and chemical resistance having. Thus, in order to impart high fluidity to polycarbonate, usually some measures taken as alloying with a styrene-based resin and Addition of a plasticizer (for example, Patent Document 1).

A Polycarbonate / polylactic acid alloy with pearly gloss and excellent fluidity and thermal and mechanical properties is known, but still exists Space for improving their impact resistance (for example, Patent Document 2).

A polycarbonate / polyester alloy generally lacks impact resistance. Conventional alloy technology provides only Izod impact strength of several kJ / m ² .

Therefore is the further improvement of the impact resistance in particular in the field of automobiles having excellent impact resistance characteristics require, necessary.

To the The purpose of improving the impact resistance is known to be the Interfacial strength an alloy by improving the compatibility of a polymer alloy elevated.

For example is a bisphenol A-type epoxy resin as a compatibilizer for polycarbonate / polyamide-polyether block copolymer used (for example, Patent Document 3).

Farther be an epoxy-modified styrene-butadiene-styrene copolymer (SBS) and a terpene phenolic resin as a compatibilizer for a polycarbonate / styrene type resin composition used (for example, Patent Document 4).

Regarding Of the systems described above, it is reported that the error is in the Appearance fixed and the impact resistance by controlling the interface conditions improved between polycarbonate and a supplementary material becomes. However, no reports have been written regarding polycarbonate / polylactic acid.

For the purpose improving the impact resistance of a polycarbonate alloy is also the addition of an acrylonitrile-butadiene-styrene block copolymer (ABS), an impact-resistant polystyrene resin, etc. proposed (for example Patent Document 5).

Each however, the systems described above lack fluidity. Height fluidity is for a thin-walled one Object that represents a new trend required. Consequently There is a need for the development of new polycarbonate resin composition.

To the The purpose of imparting high fluidity to polycarbonate may be considered Be sure to add a component that has better fluidity than polycarbonate and which is compatible with polycarbonate.

• [Patentdokument 1] Japanische geprüfte Patentveröffentlichung Nr. H07-068455
• [Patentdokument 2] Japanische ungeprüfte Patentveröffentlichung Nr. H07-109413
• [Patentdokument 3] Japanische ungeprüfte Patentveröffentlichung Nr. H07-026131
• [Patentdokument 4] Japanische ungeprüfte Patentveröffentlichung Nr. 2000-143912
• [Patentdokument 5] Japanische ungeprüfte Patentveröffentlichung Nr. 2000-169692

Polylactic acid, which is a polyester class, has excellent affinity with polycarbonate. However, since polylactic acid has poor impact resistance, its field of application is limited. For example, in the field of automobiles, an improvement in impact resistance is essential.

• [Patent Document 1] Japanese Examined Patent Publication No. H07-068455
• [Patent Document 2] Japanese Unexamined Patent Publication No. H07-109413
• [Patent Document 3] Japanese Unexamined Patent Publication No. H07-026131
• [Patent Document 4] Japanese Unexamined Patent Publication No. 2000-143912
• [Patent Document 5] Japanese Unexamined Patent Publication No. 2000-169692

epiphany the invention

One The object of the invention is the impact resistance of a polycarbonate resin / fatty acid polyester alloy without impairment their fluidity to improve, and errors in appearance, such as pearly shine and Formation of turbulence impressions, submissions.

The present inventors have carried out a comprehensive study found that a thermoplastic resin composition in which a rubbery elastomer in a predetermined amount in a resin mixture, the specific proportions of a polycarbonate resin and a fatty acid ester, compounded will meet the above goals can, and have completed the present invention.

• 1. Eine thermoplastische Harzzusammensetzung, umfassend (A) ein Harzgemisch, das (a-1) ein Polycarbonatharz in einer Menge von 45 bis 97 Masse-% und (a-2) einen Fettsäurepolyester in einer Menge von 55 bis 3 Masse-% umfasst, und (B) ein kautschukartiges Elastomer in einer Menge von 0,5 bis 20 Masseanteilen pro 100 Masseanteilen des Harzgemisches, wobei Komponente (B) in einer Grenzfläche zwischen Bestandteil (a-1) und Bestandteil (a-2) oder in Domänen von Bestandteil (a-2) dispergiert ist;
• 2. Die thermoplastische Harzzusammensetzung, wie unter 1 vorstehend aufgeführt, wobei das Polycarbonatharz von Bestandteil (a-1) ein Viskositätsmittel-Molekulargewicht im Bereich von 10000 bis 40000 aufweist;
• 3. Die thermoplastische Harzzusammensetzung, wie in 1 oder 2 vorstehend aufgeführt, wobei der Fettsäurepolyester von Bestandteil (a-2) Polymilchsäure und/oder ein Copolymer von Milchsäure und einer anderen Hydroxycarbonsäure ist;
• 4. Die thermoplastische Harzzusammensetzung, wie in einem der Punkte 1 bis 3 vorstehend aufgeführt, wobei das kautschukartige Elastomer von Komponente (B) ein kautschukartiges Elastomer ist, das mindestens ein Element enthält, ausgewählt aus Poly(methylmethacrylat), Poly(ethylmethacrylat), Poly(methylacrylat) und Poly(ethylacrylat);
• 5. Die thermoplastische Harzzusammensetzung, wie in einem der Punkte 1 bis 4 vorstehend aufgeführt, wobei das kautschukartige Elastomer von Komponente (B) einen mittleren Teilchendurchmesser von 100 bis 500 nm aufweist;
• 6. Die thermoplastische Harzzusammensetzung, wie in einem der Punkte 1 bis 5 vorstehend aufgeführt, wobei die Zusammensetzung für Büro-Automationsanlagen, Informations- und Kommunikationsgeräte, Kraftfahrzeugteile oder elektrische Haushaltsgeräte gedacht ist;
• 7. Der Formkörper aus einer thermoplastischen Harzzusammensetzung, wie in einem der Punkte 1 bis 6 vorstehend aufgeführt.

Namely, the present invention relates to:

• A thermoplastic resin composition comprising (A) a resin composition comprising (a-1) a polycarbonate resin in an amount of 45 to 97% by mass and (a-2) a fatty acid polyester in an amount of 55 to 3% by mass and (B) a rubbery elastomer in an amount of 0.5 to 20 mass parts per 100 mass parts of the resin mixture, wherein component (B) is in an interface between component (a-1) and component (a-2) or in domains of Component (a-2) is dispersed;
• 2. The thermoplastic resin composition as recited in 1 above, wherein the polycarbonate resin of component (a-1) has a viscosity average molecular weight in the range of 10,000 to 40,000;
• 3. The thermoplastic resin composition as recited in 1 or 2 above, wherein the fatty acid polyester of component (a-2) is polylactic acid and / or a copolymer of lactic acid and another hydroxycarboxylic acid;
• The thermoplastic resin composition as recited in any one of items 1 to 3 above, wherein the rubbery elastomer of component (B) is a rubbery elastomer containing at least one member selected from poly (methyl methacrylate), poly (ethyl methacrylate), poly (methyl acrylate) and poly (ethyl acrylate);
• The thermoplastic resin composition as recited in any one of items 1 to 4 above, wherein the rubbery elastomer of component (B) has an average particle diameter of 100 to 500 nm;
• The thermoplastic resin composition as recited in any one of items 1 to 5 above, wherein the composition is for office automation equipment, information and communication equipment, automotive parts or home electric appliances;
• 7. The molded article of a thermoplastic resin composition as recited in any one of items 1 to 6 above.

By Dispersion of the rubbery elastomer in an interface between the polycarbonate resin and the fatty acid polyester or in a domain of the fatty acid polyester becomes the impact resistance of the polycarbonate resin / fatty acid ester without impairment the fluidity improved. In addition, because the shape of the fatty acid polyester domains is uniform and is stabilized Defects in appearance, such as pearly gloss and turbulence impressions, are prevented become.

In addition, can the use of a polycarbonate-polyorganosiloxane copolymer the Flame retardancy as well the impact resistance improve.

Short description the drawings

1 is a transmission electron microscope photograph in Example 2.

2 is a transmission electron microscope photograph in Example 6.

Best way to carry out the invention

The The present invention will be described below in detail.

In the thermoplastic resin composition of the present invention, the polycarbonate resin constituting component (a-1) of component (A) is not particularly limited. Although various polycarbonate resins can be used, a polymer having the repeating units of the following general formula (1) is suitably used:

In the above general formula (1), R ¹ and R ^{2 are} each a halogen atom (for example, chlorine, fluorine or iodine) or a C ₁ -C ₈ alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, various butyl groups (an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group), various pentyl groups, various hexyl groups, various heptyl groups or various octyl groups). The symbols m and n are each an integer from 0 to 4. When m is 2 to 4, a plurality of R ¹ groups may be the same or different from each other. When n is 2 to 4, several R ² groups may be the same or different.

The symbol Z represents a C ₁ -C ₈ alkylene or C ₂ -C ₈ alkylidene group (such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group or an isopropylidene group, for example) C ₅ -C ₁₅ cycloalkylene or C ₅ -C ₁₅ cycloalkylidene group (such as a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group or a cyclohexylidene group, for example), a single bond, a bond of -SO ₂ -, -SO-, -S- , -O- or -CO- or a bond of the following formula (2) or formula (2 '):

wobei R¹, R², Z, m und n die gleiche Bedeutung wie diejenigen der obigen allgemeinen Formel (1) besitzen, mit einem Carbonat-Vorläufer wie Phosgen.The above polymer can usually be easily prepared by reacting a dihydric phenol represented by the following general formula (3):

wherein R ¹ , R ² , Z, m and n have the same meaning as those of the above general formula (1), with a carbonate precursor such as phosgene.

The is called, For example, the polymer may be prepared by reacting a divalent one Phenols with a carbonate precursor, like phosgene, in a solvent, such as methylene chloride, in the presence of a known acid acceptor or a known molecular weight regulator. The polymer can also be prepared by transesterification of a dihydric phenol with a carbonate precursor, as a carboxylic acid ester become.

A Variety of dihydric phenols can be considered the dihydric phenol of the above general formula (3).

Especially is 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) prefers.

Examples for the dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) alkanes, such as bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 1,2-bis (4-hydroxyphenyl) ethane; Bis (4-hydroxyphenyl) cycloalkanes as 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclodecane; 4,4'-dihydroxydiphenyl; Bis (4-hydroxyphenyl) oxide; sulfide bis (4-hydroxyphenyl); Bis (4-hydroxyphenyl) sulfone; sulfoxide bis (4-hydroxyphenyl); and bis (4-hydroxyphenyl) ketone.

In addition to Hydroquinone may be mentioned in the above dihydric phenols.

The dihydric phenols can used singly or as a mixture of two or more thereof. As carboxylic ester compound can for example, diaryl carbonates, such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The Polycarbonate resin may be a homopolymer using one of the mentioned above dihydric phenols or may be a copolymer using two or more of the above be dihydric phenols.

Farther For example, the polycarbonate resin may be a thermoplastic randomly branched one Polycarbonate resin, which is made using a polyfunctional aromatic compound together with the above-mentioned divalent Phenol available is.

Specific examples for such a polyfunctional aromatic compound, generally Chain branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl. Α- (4'-hydroxyphenyl) ethyl] -4- [α, α'-bis (4 "-hydroxyphenyl) ethyl] benzene, phloroglucin, trimellitic or isatin-bis (o-cresol).

The Polycarbonate resin having the above features is commercially available, for example as an aromatic polycarbonate resin, such as TAFLON, FN3000A, FN2500A, FN2200A, FN1900A, FN1700A and FN1500A (Trademarks, manufactured from Idemitsu Kosan Co., Ltd.).

When The polycarbonate resin used in the present invention may additionally to a homopolymer obtained by using the above-mentioned bivalent Phenol is produced alone, a polycarbonate-polyorganosiloxane copolymer (hereinafter referred to as PC-POS copolymer) may be mentioned, for reasons of higher impact resistance and improved flame retardancy is preferred is.

wobei R¹, R², Z, m und n die gleiche Bedeutung wie vorstehend besitzen und
einer Polyorganosiloxangruppierung, die Wiederholungseinheiten mit einer durch die folgende allgemeine Formel (4) dargestellten Struktur enthält:

wobei R³, R⁴ und R⁵ jeweils ein Wasserstoffatom, eine C₁- bis C₅-Alkylgruppe (beispielsweise eine Methylgruppe, eine Ethylgruppe, eine Propylgruppe, eine n-Butylgruppe oder eine Isobutylgruppe) oder eine Phenylgruppe sind und p und q jeweils eine ganze Zahl von 0 oder mindestens 1 sind, mit der Maßgabe, dass eine Summe von p und q eine ganze Zahl von mindestens 1 ist.Although various types of PC-POS copolymers exist, the preferable one is a copolymer consisting of a polycarbonate component containing recurring units having a structure represented by the formula (1):

wherein R ¹ , R ² , Z, m and n have the same meaning as above, and
a polyorganosiloxane group containing repeating units having a structure represented by the following general formula (4):

wherein R ³ , R ⁴ and R ^{5 are} each a hydrogen atom, a C ₁ to C ₅ alkyl group (for example, a methyl group, an ethyl group, a propyl group, a n-butyl group or an isobutyl group) or a phenyl group, and p and q each are an integer of 0 or at least 1, with the proviso that a sum of p and q is an integer of at least one.

Of the Degree of polymerization of the polycarbonate component is here preferably 3 to 100, and the degree of polymerization of the polyorganosiloxane component is preferably 2 to 500.

The PC-POS copolymer described above is a block copolymer, consisting of the polycarbonate component with those through the top mentioned general formula 1 represented repeating units and the Polyorganosiloxane component with those in the above-mentioned general Formula (4) repeating units shown.

One such PC-POS copolymer can be prepared, for example by dissolving a previously prepared polycarbonate oligomer (abbreviated as PC oligomer) constituting the polycarbonate component and a polyorganosiloxane (for example polydialkylsiloxane, such as polydimethylsiloxane (PDMS) and polydiethylsiloxane, and polymethylphenylsiloxane etc.) which is to build up the polyorganosiloxane component and which is a terminal having reactive group in a solvent such as methylene chloride, Chlorobenzene or chloroform, and performing with the resulting Solution, after the addition of a solution of bisphenol in aqueous Sodium hydroxide, an interfacial polymerization in the presence of a catalyst, such as triethylamine, trimethylbenzylammonium chloride Etc.

One PC-POS copolymer produced by a method described in Japanese Patent publication No. S44-30105 or Japanese Patent Publication No. S45-20510 can be also used.

The PC oligomer having the structure represented by the general formula (1) Repeating units can be easily prepared by a solvent method wherein a represented by the above general formula (3) dihydric phenol with a carbonate precursor, such as phosgene, and a Carbonsäureesterverbindung in a solvent, such as methylene chloride, in the presence of a known acid receptor and a known molecular weight regulator.

For example For example, the PC oligomer can be made by reacting a dihydric phenol with a carbonate precursor, such as phosgene, or by transesterification of a carbonate precursor, such as a carboxylic ester compound, with a dihydric phenol in a solvent such as methylene chloride, in the presence of a known acid receptor and a known molecular weight regulator.

When Carbonsäureesterverbindung can be similar Compounds such as those described above can be used. As a molecular weight regulator can be similar Compounds such as those described below may be used.

The PC oligomer used in the preparation of the PC-POS copolymer may be a homopolymer using a the dihydric phenols described above are obtained, or it can be one using two or more of them be obtained copolymer.

Farther For example, the PC oligomer may be a thermoplastic, randomly branched one Polycarbonate resin, which is made using a polyfunctional aromatic compound in combination with the one described above dihydric phenol was obtained.

wobei R⁶ eine C₁- bis C₃₅-Alkylgruppe ist und a eine ganze Zahl von 0 bis 5 ist.In addition, the polycarbonate resin used in the present invention may conveniently be a polycarbonate resin having a terminal group represented by the general formula (5):

wherein R ^{6 is} a C ₁ to C ₃₅ alkyl group and a is an integer of 0 to 5.

In the general formula (5), R _{6 is} a C ₁ to C ₃₅ alkyl group which may be linear or branched.

The Position of the link can be a p-position, m-position and o-position, though preferably a p-position.

The Polycarbonate resin of the general formula (5) can be easily converted a dihydric phenol with phosgene or a carboxylic acid ester compound getting produced.

For example For example, the polycarbonate resin may be prepared by reacting a dihydric phenol with a carbonate precursor, such as phosgene, in the presence of a catalyst such as triethylamine, and a special terminating agent or by transesterification a carbonate precursor, such as diphenyl carbonate, with a dihydric phenol in a solvent, such as methylene chloride.

The Dihydric phenol may be a compound that is the same or different is from that represented by the above general formula (3) Connection.

The Polycarbonate resin may be a homopolymer prepared by using a the dihydric phenols described above are obtained, or a copolymer made using two or more be obtained from them.

The Polycarbonate resin may also be a thermoplastic, randomly branched Polycarbonate, which consists of the above dihydric phenol and a polyfunctional aromatic compound is produced.

When the carboxylic acid ester compound can Diaryl carbonates, such as diphenyl carbonate, and dialkyl carbonates, such as Dimethyl carbonate and diethyl carbonate.

When The terminating agent may be a phenolic compound that is capable of is, a terminal, represented by the general formula (5) Group to be used.

dargestellt, wobei R⁶ die gleiche Bedeutung wie vorstehend besitzt.Namely, the phenol compound is represented by the general formula (6)

in which R ^{6 has} the same meaning as above.

When Alkylphenol can mentioned phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, docosylphenol, tetracosylphenol, hexacosylphenol, Octacosylphenol, triacontylphenol, dotriacontylphenol and tetratriacontylphenol.

These Alkylphenols can used singly or in combination of two or more thereof.

These Alkylphenols can used in conjunction with another phenolic compound, etc. as long as the effect of the present invention is not impaired.

The Polycarbonate resin produced by the above method has practical at its one end or at both ends of the molecule one terminal group represented by the general formula (5).

The Polycarbonate resin used as component (a-1) has a viscosity average molecular weight of usually 10,000 to 40,000.

If the viscosity agent of the molecular weight is 10,000 or more, the obtained thermoplastic provides Resin composition sufficient heat resistance and mechanical properties. If the viscosity average molecular weight 40,000 or less provides the obtained thermoplastic resin composition an improved shape processability.

The Viscosity-average molecular weight of the polycarbonate resin preferably 14000 to 25000, stronger preferably 15,000 to 22,000.

The Viscosity-average molecular weight (Mv) is determined as follows.

The viscosity of a solution of the polycarbonate resin in methylene chloride at 20 ° C is measured using an Ubbelohde viscometer, from which the intrinsic viscosity [η] is determined. The Mv is calculated from the following equation: [η] = 1.23 × 10 -5 mv 0.83

In the thermoplastic invention Resin composition may be polylactic acid or a copolymer of polylactic acid with hydroxycarboxylic acid expediently as fatty acid polyester of component (a-2) of component (A).

Polylactic acid can be synthesized from a cyclic dimer of lactic acid, which generally called lactide. Process for the preparation of polylactic acid are described in U.S. Patent No. 1,995,970, U.S. Pat. 2,362.51 1, U.S. Patent No. 2,683,136, etc.

One Copolymer of lactic acid with another hydroxycarboxylic acid can usually by ring-opening polymerization of lactide and a cyclic ester intermediate of a hydroxycarboxylic acid become. Process for the preparation of such a copolymer are For example, U.S. Patent No. 3,635,956, U.S. Patent No. 3,797,499, etc.

If one on lactic acid based resin by direct dehydrative polycondensation instead by ring-opening polymerization is produced are lactic acid and, if necessary, the other hydroxycarboxylic acid of an azeotropic dehydrating one Condensation, preferably in an organic solvent, especially a phenyl ether solvent, subjected. In this case, it is particularly preferable that the Polymerization is carried out by a method in which the by Azeotropic distillation obtained solvents for removal is treated by water, and the resulting, essentially anhydrous solvents is returned to the reaction system.

The thus obtained lactic acid resin has a degree of polymerization suitable for the present invention is.

When Lactic acid which is used as the raw material may include L-lactic acid, D-lactic acid Mixture thereof or lactide, which is a dimer of lactic acid, be.

When other hydroxyl carboxylic acids, which in conjunction with lactic acid can be used glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid and 5-hydroxyvaleric acid and 6-Hycroxycapronsäure mentioned become. Furthermore you can also cyclic ester intermediates of hydroxycarboxylic acids, such as Glycolide, which is a dimer of glycolic acid, and α-caprolactone, which a cyclic ester of 6-hydroxycaproic acid.

at the production of the lactic acid resin Is it possible, expediently a molecular weight regulator, a branching agent and others adding modifying agents.

The lactic acids and hydroxycarboxylic acids as components of the copolymer used singly or in combination of two or more thereof become. Furthermore you can two or more lactic acid resins be used as a mixture.

The fatty acid polyester of the component (a-2) of the present invention has the thermi preferably high molecular weight and thus preferably has a weight average molecular weight of 30,000 or more.

When fatty acid polyester is polylactic acid from the point of view of durability and rigidity.

at the resin mixture according to the invention is the proportion, based on the mass ratio of the polycarbonate resin as component (a-1) to the fatty acid polyester as a component (a-2) in the range of 45:55 to 97: 3, preferably 60:40 to 90:10.

If the proportion of the components (a-1) and (a-2) within the above Area owns, has the thermoplastic resin composition according to the invention good mechanical strength, heat resistance and fluidity.

In the thermoplastic invention Resin composition becomes the rubbery elastomer of component (B) used for the purpose of improving the impact resistance and is, from the standpoint of improved impact resistance and dimensional stability of the fatty acid ester, in particular the polylactic acid domains, preferably a rubbery core-shell sample elastomer.

The rubbery grafted paste preferably has a shell acrylic structure having high affinity with polylactic acid, so that it is selective in the fatty acid polyester, especially in the polylactic acid domains can be.

The rubbery elastomer has an average particle diameter from 100 to 500 nm, preferably 200 to 400 nm.

If the average particle diameter of the rubbery elastomer Within the above range, the elastomer has excellent Dispersibility, giving the effect of improving the impact resistance is high.

The rubbery core-shell grafted paste has a two-layered structure, composed of a core and a shell.

Conveniently, is used a rubbery Pfropfelastomer, in the form of powder (in the form of particles) and of a rubbery one Core and a hard resinous shell, with which the surface of the Core part is provided.

One greater Proportion of the rubbery core-shell sample elastomer may be its original maintain powdery shape, even after mixing with the resin mixture of the polycarbonate resin and the fatty acid polyester is, and therefore can be uniform in one interface between the polycarbonate resin and the polylactic acid or in domains of polylactic acid be dispersed. That's why Defects in appearance, such as pearly gloss and turbulence impressions, avoided become.

When Rubbery core-shell sample elastomer is suitably used a product obtained by polymerizing one or at least two vinyl monomers, such as styrene, in the presence of one or at least two rubbery graft polymers obtainable from monomers, the main ones for example, alkyl acrylate or alkyl methacrylate and dimethylsiloxane exist, used.

As the alkyl acrylates and alkyl methacrylates, those having C ₂ to C ₁₀ alkyl groups can be used. For example, a product obtainable using methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate or n-octyl methacrylate is preferable. Particularly preferred is a product obtainable using methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate.

The using the mainly composed of alkyl acrylate or the like monomer component The elastomer obtained may preferably be a copolymer obtained by Reaction of 70% by weight or more of an alkyl acrylate with 30% by weight or less of another vinyl monomer with the alkyl acrylate is copolymerizable, such as alkyl acrylates, such as methyl methacrylate, Acrylonitrile, vinyl acetate and styrene.

Furthermore, the copolymer may be reacted with a polyfunctional compound such as divinylbenzene, ethylene di methacrylate, triallyl cyanurate and triallyl isocyanurate.

The rubbery elastomer may be a product obtained by polymerizing or copolymerizing an aromatic vinyl compound such as styrene and α-methylstyrene, an acrylic ester such as methyl acrylate and ethyl acrylate, or one Methacrylesters, such as methyl methacrylate and ethyl methacrylate, in Presence of the rubbery graft polymer is obtained.

Farther can these monomers together with another vinyl monomer, such as Vinyl cyanide compound, e.g. As acrylonitrile or methacrylonitrile, or a vinyl ester compound, e.g. Vinyl acetate or vinyl propionate, used to make a copolymer.

These Polymers and copolymers can a by various methods, such as bulk polymerization, suspension polymerization and emulsion polymerization. Among them are polymers and copolymers obtained by the emulsion polymerization are obtained, particularly preferably used.

Farther For example, as the rubbery core-shell grafted paste, a MAS resin elastomer obtained by Graft copolymerization of 20 to 40% by weight of styrene and methyl acrylate with 60 to 80% by mass of n-butyl acrylate polymer is used become.

In addition will a composite rubber graft copolymer obtained by graft copolymerization of at least one vinyl monomer with a composite rubber of a average particle size of about 0.01 to 1 μm and having a structure in which 5 to 95 mass% a polysiloxane rubber component inseparable with 95 to 5 mass% of a poly (meth) acrylate rubber component are manufactured.

Under These rubbery core-shell graft elastomers with various types Structures are available commercially KM-357P (manufactured by Rohm & Haas Company) and METABLEN W450A, METABLEN W529, METABLEN S2001, METABLEN C223, KS3406 (manufactured by Mitsubishi Rayon Co., Ltd.).

By the way have noted rubbery elastomers, such as polyamide-polyether block copolymers, the have no core-shell structure, a large form factor that has a big impact on the impact resistance, and they are therefore for the purpose of the present invention is not preferred.

The Compounding amount of the rubbery elastomer, which component B represents is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass per 100 parts by mass of the resin mixture, represents component A.

If the compounding amount within the range described above the impact resistance is improved without the fluidity improving Effect of polylactic acid to impair.

The The present invention also provides a molded article of the type described above Resin composition ready.

The thermoplastic according to the invention Resin composition can be prepared by mixing and kneading the above Component (a-1), Component (a-2), Component (B) and, if necessary, other ingredients are obtained.

One Such mixing and kneading can be done in a commonly used method carried out be, for example, using a method that has a Ribbon mixer, a Henschel mixer, a Banbury mixer, one Drum spin, a single-axis screw extruder, a twin-axis screw extruder, a co-kneader, a multi-axis screw extruder or the like is used.

The Heating temperature for the kneading is usually selected from a range of 220 to 260 ° C.

The Temperature at which the thermoplastic resin composition of the present invention Shaping is also usually from a range of 220 to 260 ° C selected.

Examples

The The present invention will be next in more detail with reference to some examples. However, that is the present invention by no means limited to these examples.

Production Example 1

[Production of PC-2; PC-PDMS (polydimethylsiloxane) copolymer]

(1) Preparation of the PC oligomer

In 400 liters of an aqueous 5% by mass of sodium hydroxide solution 60 kg of bisphenol A were dissolved, around a watery sodium hydroxide of Bisphenol A. Subsequently, the aqueous sodium hydroxide solution of Bisphenol A, which was kept at room temperature, and methylene chloride via an orifice with flow rates of 138 l / h or 69 l / h in a tubular reactor with an inner diameter of 10 mm and one tube length initiated by 10 m, in the same time phosgene with a flow velocity of 10.7 kg / h was blown in, allowing the reaction 3 hours long continuous has been.

Of the Tubular reactor used here was a double-walled tube, and cooling water was sent through its shell part, so that the temperature held therefrom the reaction liquid at 25 ° C. has been.

Of the pH of the discharged liquid was set between 10 and 11.

The thus obtained reaction liquid was left quiet. An aqueous phase was separated and removed to collect a methylene chloride phase (220 L) and to obtain PC oligomer (concentration: 317 g / l).

It It was found that the PC oligomer thus obtained a degree of polymerization in the range of 2 to 4 and a concentration of chloroformate groups of 0.7 mol / l.

(2) Preparation of reactive PDMS

1483 g octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% by mass of sulfuric acid were mixed and stirred at room temperature for 17 h.

Subsequently was the oil phase separated, and 25 g of sodium bicarbonate were added. The Mixture was stirred for 1 h.

To the filtration became the oil phase at 150 ° C vacuum distilled under a pressure of 3 Torr (400 Pa) to low to remove boiling components and to obtain an oily product.

294 g of the oily one obtained above Products were in the form of a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum of a platinum chloride-alcoholate complex at a temperature of 90 ° C added.

The resulting mixture was stirred for 3 h while the temperature was between 90 and 1 15 ° C was held.

The Reaction product was extracted with methylene chloride, and the extract was washed three times with water 80% by mass of methanol to remove excess 2-allylphenol.

The Product was over dried anhydrous sodium sulfate, and then the solvent under vacuum by heating at 115 ° C away.

It It was found that the thus obtained reactive PDMS, with Phenol terminated, according to NMR measurement 30 Dimethylsilanoxy repeat units had.

(3) Preparation of the PC-PDMS copolymer

138 g reactive PDMS obtained in (2) above in 2 l of methylene chloride, including 10 l of the PC oligomer obtained in (1) above were.

the resulting mixture was a solution of 26 g of sodium hydroxide, solved in 1 liter of water, and 5.7 ml of triethylamine, and the mixture was reacted at room temperature for 1 hour with stirring at 500 rpm.

To Completion of the reaction was a solution of 600 g of bisphenol A, solved in 5 l of an aqueous 5.2 Mass% sodium hydroxide solution, 8 l of methylene chloride and 96 g of p-tert-butylphenol was added to the above reaction system, and the mixture was allowed to stand for 2 hours with stirring reacted at 500 U / min at room temperature.

To Upon completion of the reaction, 5 l of methylene chloride were added to the reaction mixture added. Subsequently The mixture was washed successively with 5 L of water, 5 L of a brine (0.03 mol / l aqueous Sodium hydroxide) 5 l of an acid (0.2 mol / l hydrochloric acid) and 5 liters of water (twice) in this order. Finally became Methylene chloride is removed to PC-PDMS copolymer in the form of flakes to obtain.

The thus obtained PC-PDMS copolymer was vacuum dried at 120 ° C for 24 h.

It It was found that the copolymer has a viscosity average molecular weight of 17000 and has a PDMS content of 4.0% by mass.

The PDMS content was determined as follows:

The content was determined on the basis of an intensity ratio of the peak at 1.7 ppm attributed to the methyl group of the isopropyl group of bisphenol A to the peak at 0.2 ppm attributed to the methyl group of the dimethylsiloxane in ¹ H-NMR ,

Production Example 2

[Production of PC-3]

(1) Preparation of alkylphenol (A)

In one with a baffle and stirring blades equipped reaction reactor materials were submitted, the 300 parts by mass of phenol and 110 parts by mass of a 1-docosene (Phenol / olefin mole ratio = 9/1) and 11 mass fractions of a strongly acidic, polystyrene-based, sulfonic acid cation exchange resin (Amberlyst 15, available from Rohm & Haas Co., Ltd.) as a catalyst. The mixture was then added 120 ° C 3 h with stirring implemented.

To Completion of the reaction was the product by vacuum distillation purified to obtain alkylphenol (a).

It it was found that the number of carbon atoms of the alkyl group of the obtained alkylphenol (a) is 22.

(2) Preparation of the PC oligomer

In 400 l of an aqueous 5% by mass of sodium hydroxide solution 60 kg of bisphenol A were dissolved, around a watery sodium hydroxide of Bisphenol A.

Subsequently were the watery sodium hydroxide of bisphenol A, which was kept at room temperature, and methylene chloride over one Throttle plate with flow rates of 138 l / h or 69 l / h in a tubular reactor with an inner diameter of 10 mm and one tube length initiated by 10 m, in the same time phosgene with a flow velocity of 10.7 kg / h was blown in, allowing the reaction 3 hours long continuous has been.

The tube reactor used here was a double-walled tube, and cooling water was through its Passed jacket part, so that the temperature of the discharged therefrom reaction liquid was kept at 25 ° C.

Of the pH of the discharged liquid was set between 10 and 11.

The thus obtained reaction liquid was left quiet. An aqueous phase was separated and removed to collect a methylene chloride phase (220 L) and to obtain PC oligomer (concentration: 317 g / l).

It It was found that the PC oligomer thus obtained a degree of polymerization in the range of 2 to 4 and a concentration of chloroformate groups of 0.7 mol / l.

(3) Final modified polycarbonate resin

In a vessel with a Internal volume of 50 l and equipped with a stirrer were 10 l of the PC oligomer obtained in (2) above, in the 249 g of alkylphenol (a) obtained in (1) above were dissolved.

the The resulting mixture was added with an aqueous sodium hydroxide solution (53 g sodium hydroxide, dissolved in 1 liter of water) and 5.8 ml of triethylamine, and the mixture was stirred for 1 h implemented at 300 rpm.

Subsequently was the above reaction system with a solution of bisphenol A dissolved in an aqueous sodium hydroxide (Bisphenol A: 720 g, sodium hydroxide: 412 g, water: 5.5 l), and 8 liters of methylene chloride were added. The mixture was then 1 h with stirring reacted at 500 rpm.

To Completing the reaction, the reaction mixture 7 l of methylene chloride and 5 l of water added. The mixture was stirred at 500 rpm for 10 minutes touched and subsequently for separation into an organic phase and an aqueous phase quietly left.

The The organic phase thus obtained was washed successively with 5 l of a brine (0.03 mol / l NaOH), 5 l of an acid (0.2 mol / l HCl) and 5 l of water (twice) in this order.

After that methylene chloride was removed by distillation to give a polymer in the form of flakes.

It It was found that the polymer has a viscosity average molecular weight of 17500 had.

Examples 1 to 9 and Comparative Examples 1 to 8

The Ingredients and components were as described in Table 1-1 and Table 1-2 parts mixed, a vented twin-screw extruder (Model: TEM35, manufactured by Toshiba Machine Co., Ltd.), melted and at 240 ° C kneaded and then pelleted.

at all Examples and Comparative Examples, a phosphorus type antioxidant (trademark: ADEKASTAB PEP36, manufactured by Adeka Corporation) and a phenol-type antioxidant (Trademark: IRGANOX 1076, manufactured by Chiba Specialty Chemicals Inc.) as a stabilizer each in an amount of 0.1 Added by mass.

The resulting pellets were dried for 10 h at 100 ° C and then by Injection molding at an injection molding temperature from 240 ° C (Temperature of the molds: 40 ° C) Press-formed to test specimen receive.

The Test specimens were each to the appropriate properties according to the various below assessed evaluation tests. The results are in table 1-1 and Table 1-2.

Photographs of the products of Examples 2 and 6 were taken using a transmission electron microscope (TEM) and were as in Figs 1 and 2 shown. In the photographs, the dark pattern indicates the polycarbonate resin, the white pattern indicates the polylactic acid, and the black spots in the white pattern indicate the rubbery elastomer.

The Ingredients and components used for mixing and for performance evaluation procedures used are as follows:

[Compounded ingredients and components]

Component (a-1):

• (a): (PC-1); Polycarbonate resin, FN1700A (manufactured from Idemitsu Kosan Co., Ltd., Bisphenol A Polycarbonate Resin, Viscosity Molecular Weight: 17500, molecular end: p-tert-Butylphenolrest)
• (b): (PC-2); Polycarbonate-polydimethylsiloxane-bisphenol-A-polycarbonate resin (PC-PDMS), (see Production Example 1)
• (c): (PC-3); end-modified polycarbonate resin (see Preparation Example 2)

Component (a-2):

• PLA; polylactic acid, H 100 (manufactured by Mitsui Chemical Corporation)

Component B:

• (a) rubbery elastomer-1; Acrylic / acrylate elastomer, W450A, manufactured by Mitsubishi Rayon Co., Ltd.
• (b) rubbery elastomer-2; glycidylmethacrylatmodifiziertes elastomer; KS3406, manufactured by Mitsubishi Rayon Co., Ltd.
• (c) rubbery elastomer-3; Polyamide / polyether block copolymer PEBAX4011, manufactured by Elfatochem Japan Inc.

[Performance Evaluation Method]

• (1) IZOD (IZOD impact strength): Measured according to ASTM D256 using a test piece having a thickness of 3.18 mm, at 23 ° C; Unit: kJ / m ²
• (2) fluidity (SFL): measured using an injection molding temperature of 260 ° C, a Mold temperature of 80 ° C, a wall thickness of 2 mm, a width of 10 mm of an injection pressure of 7.85 MPa; Unit: cm
• (3) flame retardancy: UL94 Default; specimen thickness: 3.0 mm; vertical flammability tests were performed according to test 94 conducted by Underwriters Laboratories, Inc.
• (4) Appearance of molded article: A square plate of 100 × 100 × 2 mm was produced by compression molding, and the sample was with the bare one Eye judged by the following reviews: B: slightly uneven River A: no uneven river

Out Table 1-1 and Table 1-2 show the following facts:

(1) Examples 1 to 9

By Compounding a resin mixture of polycarbonate resin and polylactic acid with a rubbery core-shell elastomer improves the Izod impact strength significant.

Like from the 1 and 2 As is apparent, when the shell is made of a rubbery elastomer having an acrylic structure, the rubbery elastomer is dispersed in an interface between the polycarbonate resin and the polylactic acid particularly in the polylactic acid domains. Therefore, the shape of the polylactic acid domains becomes uniform and stabilized. Thus, it is possible to obtain a thermoplastic resin composition which is excellent in impact resistance and which retains the high fluidity of the polycarbonate resin / polylactic acid. In addition, the molded article obtained from such a composition has a good appearance.

The rubbery core-shell elastomer is extremely effective for improving the impact resistance, and the compounding amount thereof is considered to be a small amount reduced.

Under Use of the polycarbonate-polyorganosiloxane will not only be the Impact resistance but also improves the flame retardancy. Besides that is it is possible a shaped body to get a good look.

(2) Comparative Example 1, Comparative Example 2 and Comparative Example 4

Becomes the rubbery elastomer in a small amount or at all Not used, the impact resistance becomes low.

(3) Comparative Example 3

Becomes the rubbery elastomer in an amount of 30% by mass or more used is the fluidity significantly reduced.

(4) Comparative Example 5 and Comparative Example 8

exceeds the compounding amount of polylactic acid 50% by mass, is the impact strength improving Low effect due to compounding of the rubbery elastomer.

(5) Comparative Example 6 and Comparative Example 7

has the rubbery elastomer is not an acrylic structure, is the Impact resistance improving effect when used in the same Quantity low. Consequently, the form of the polylactic acid domains does not become stabilized. As a consequence, due to the bad form fluidity Turbulence marks.

[Industrial application]

It is according to the invention possible, to obtain a thermoplastic resin composition having high impact properties has high fluidity, and which fixes the flaws in appearance, such as pearly gloss and turbulence impressions. The thermoplastic resin composition is in the field of electrical and electronic equipment, such as office automation equipment, information and communication devices and electrical household appliances, in the field of motor vehicles, in the construction sector, etc. applicable.

Summary

The The present invention provides a thermoplastic resin composition containing (A) a resin composition comprising (a-1) a polycarbonate resin in an amount of 45 to 97% by mass and (a-2) a fatty acid polyester in an amount of 55 to 3 mass%, and (B) a rubbery one Elastomer in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the resin mixture, wherein component (B) is in an interface between Component (a-1) and Component (a-2) or in domains of Component (a-2) is dispersed. The composition has high Impact resistance features and high fluidity, and fixes the errors in appearance, such as pearly gloss and turbulence impressions.

Claims (7)

Thermoplastic resin composition comprising: (A) a resin composition comprising (a-1) a polycarbonate resin in an amount from 45 to 97% by mass and (a-2) a fatty acid polyester in an amount from 55 to 3 mass% and (B) a rubbery elastomer in an amount of 0.5 to 20 parts by mass per 100 parts by mass of Resin mixture, wherein component (B) in an interface between Component (a-1) and Component (a-2) or in domains of Component (a-2) is dispersed. Thermoplastic resin composition according to claim 1, wherein the polycarbonate resin of component (a-1) has a viscosity average molecular weight ranging from 10,000 to 40,000. Thermoplastic resin composition according to claim 1 or 2, wherein the fatty acid polyester of component (a-2) polylactic acid and / or a copolymer of lactic acid and another hydroxycarboxylic acid. Thermoplastic resin composition according to any one of claims 1 to 3, wherein the rubbery elastomer of component (B) a rubbery elastomer containing at least one element selected from Poly (methyl methacrylate), poly (ethyl methacrylate), poly (methyl acrylate) and poly (ethyl acrylate). Thermoplastic resin composition according to any one of claims 1 to 4, wherein the rubbery elastomer of component (B) has an average particle diameter of 100 to 500 nm. Thermoplastic resin composition according to any one of claims 1 to 5, the composition for office automation equipment, information and communication devices, Automotive parts or household electrical appliances is suitable. moldings of a thermoplastic resin composition according to any one of claims 1 to 6th